Halo imide fire retardant compositions

ABSTRACT

Fire retarding agents having the structure of substituted imides, with the imide portion derived from a halogenated DielsAlder adduct of an unsaturated carboxylic compound such as maleic anhydride and a diene such as cyclopentadiene and the substituent group on the nitrogen being alkyl or aromatic, are useful in flame retardant plastic compositions.

States Patent 1 Dot'so'ii, Jr. et a].

[ Sept. 2, 1975 HALO IMIDE FIRE RETARDANT COMPOSITIONS [75] Inventors: Anderson O. Dotson, Jr.. New

Brunswick; Jack Newcombe: Lionel T. Wolford. both of Freehold. all of NJ.

[73] Assignee: Cities Service ()il Company, Tulsa.

Okla.

[22] Filed: Sept. 5. I973 [21] Appl. No.: 394,960

Related US. Application Data [62] Division of Ser. No. 183.696. Sept. 24. 1971. Pat.

52 us. Cl. 260/326 c; 260/326 H 51 Int. cl. c071) 209/34; c071) 405/02 58 Field of Search 260/326 c. 326 HL [561 References Cited UNITED STATES PATENTS 2.795.589 6/1957 Blucstonc 260/326 C 3.574.230 4/1971 Cyba 260/326 C 3.730.942 5/1973 Green 260/326 C 3.784.509 1/1974 Dotson. .lr 26()/45.75 B

OTHER PUBLICATIONS Vereschagin. A. N. et al.. Chem. Abs. 79. 104632e. (1973)QD1A6.

Primary E.\aminir-Donald G. Daus Asxis'tant E.\-umiiierMark L. Berch Attorney. Agent. or Firm-Patricia J. Hogan [57] ABSTRACT 10 Claims, N0 Drawings IMIDE FIRE RETARDANT COMPOSITIONS This is a division of application Ser. No. 183.696. filedSept.,24. l97l. now US. Pat. No. 3.784.509.

,BACKGROUND OF THE INVENTION alkenyl. aryl. alkaryl. aralkyl or cycloaliphatic. and halogenated substituents thereof. The term halogen". as used herein. means bromine or chlorine.

2. Description of the Prior Art There is a growingawareness of the need to render normallyflammable organic materials less combustible. A particularly acute need has been recognized for means of preparing solid synthetic polymers which are fire retardant or flame resistant. particularly when such polymers are to be employed in building construction or furnishing or in wearing apparel. .The prior art attempts to reduce combustibility of such compositions by the incorporation of additives have succeeded in varying degrees in achieving acceptable levels of flame resistance; however, this has invariably been accompanied by degradation of one or more of the desirable properties of the polymer. This is usually due to the loading of additives that is required to achieve adequate level of fire retardancy. but is often the result of such factors as the migratory properties-or high volatility of the additive or the instability of the additive at conventional: plastic molding temperatures. Typical prior art additives are described in US. Pat. Nos. 3,093,599. 3.385.819 and 3.456.022.

- SUMMARY It has now been discovered that compounds having the structure of a substituted imide. wherein the imide wherein Y has one of the structures Hal where R H or -CH;. and X -H or Hal and wherein Z is hydrogen. alkyl. alkenyl. aryl. alkaryl. aralkyl or cyeloaliphatic and halogenated derivatives thereof. Hal halogen. These fire retarding agents are effective in surprisingly low concentrations in organic compositions and are relatively insensitive to environmental conditions to which such compositions would ordinarily be exposed. Broadly. this invention is a fire retardant composition comprising a normally flammable organic material and an effective amount of a fire retarding agent having the structure of a substituted imide. wherein the imide is derived froma halogenated Diels-Alder adduct of an unsaturated dicarboxylic acid or anhydride and a dicne. and wherein the substituent group on the nitrogen is hydrogen. alkyl. alkenyl. aryl. alkaryl. aralkyl. or eycloaliphatic group and halogenated substituents thereof. Another portion of the invention is the novel imide itself. as above defined.

DESCRIPTION OF THE INVENTION The aforementioned fire retarding agents. which are suitable for incorporation in compositions of this invention. can be prepared by a variety of procedures. Broadly. the substituted imide is composed of two parts. a Diels-Alder portion and an amine portion. The halogenated Diels-Alder portion can be prepared by reacting an unsaturated dicarboxylie anhydride such as maleic anhydride with a diene such as cyclopentadiene. followed by halogenation of the unsaturation bond. Or. the Diels-Alder adduct may be formed by reacting a diene. such as a polyhalocyclopentadiene. with an unsaturated dicarboxylic anhydride. such as maleic anhy dride. The anhydride portion of the adduct can be transformed to an imide group. This imide can be reacted. as a variation of the Gabriel synthesis. to give a hydrocarbyl group attached to the nitrogen. Or. ammonia or a primary amine. such as RNH- can be reacted directly with the anhydride portion of the adduct to give an imide or an N-substituted imide. lmides can be prepared by a variety of methods. One general method is to react a dicarboxylic acid. such as succinic acid. with ammonia. The resultant intermediate. ammonium succinate. decomposes during distillation to give succinimide. .Another preparation is to heat phthalic anhy dride with ammonium hydroxide until a homogeneous melt of phthalimide is obtained. Nitrogen-substituted imides can be formed by substituting a suitable group for the imide hydrogen. One method is to dissolve the imide. such as phthalimide. in a suitable solvent. such as ethanol. and to add KOH. forming the potassium imide. Then. a halogen-containing compound. such as ethylene dibromide. is added and heated. forming a substituted imide. such as crude B-Bromoethylphthalimide. which is then purified. Another method is to react an amino-containing compound. such as aniline. with an acid anhydride. such as citraconic anhydride. If the hydrocarbyl group attached to the nitrogen con' tains unsaturation. halogen can be added to this unsatu ration. resulting in a compound containing halogen in the adduct portion and in the nitrogen substituent portion. The halogens in these separate portions can be the same halogen or mixed halogens. such as chlorine in one portion and bromine in the other portion.

dibromopropyl.

The substituted imide can be formed from a reaction involving a dibasic acid or an acid anhydride. Maleic anhydride is the preferred dienophile used in preparing the Diels-Alder precursor compound. but an alkylsubstituted malcic anhydride, such'as citraconic anhydride. can also be used. In similar fashion. maleic acid can be used to form the adduct. since the transforma- ,'tion from the acid to the anhydride is relatively easy.

the Diels-Alder adduet. Alkyl cyelopentadienes. such as methyl cyclopcntadiene. are also commercially available. and can be used. As previously mentioned. the halogen in the adduct portion of this compound can be added after the Diels-Aldcr adduct is formed. or the halogen can be a part of the substituted diene before the adduct is formed. Although cyclopcntadiene is representative of the preferred type of dienes used in the preparation of the various fire retarding agent. substituted dicncs. such as .furan, in which oxygen is substituted for a -CH group in cyclopentadiene. can also be used.

The substituent group on the imide nitrogen is. broadly. a hydrocarbyl or substituted hydrocarbyl group. Examples of these groupings. with specific compounds. are:

alkyl ethyl or hcxyl alkenyl allyl z i'yl phenyl alkaryl benzyl aralkyl tolyl or xylyl aralkenyl styryl cycloalkyl cyclooctyl cycloalkenyl c \'clooctcn \'l and halogenated substituents of the above. such as 2.3- Z-bromoallyl. 2-chloro-4-mcthylbenzyl. 2-methyl-4-ehlorophenyl. ,B-bromostyryl. pbromophenyl. chlorocyclohexyl and chlorcyclohexenyl. Broadly. the imides of this invention may be generally described as N-( hydrogen or polyhalopolyhydropolycyclicdicarboxylic imides.

The fire retarding agents described herein may be employed to reduce the flammability of any normally flammable or synthetic organic material. including cotton. wool. silk. paper. natural rubber. wood and paint, and are particularly effective in compositions of solid synthetic polymers. Illustrative of such polymers are the high molecular weight homopolymers and copolymers of unsaturated aliphatic and aromatic hydrocar bons. such as ethylene, propylene and styrene; acrylic polymers, such as polyacrylonitrile and poly(methyl methacrylate); alkyd resins; cellulose derivatives, such as cellulose acetate and methyl cellulose; epoxy resins; furan resins; isocyanate resins. such as the polyurethanes, melamine resins; polyamide polymers. such as nylon-6 and nylon-66; polyester resins; vinyl resins. such as (poly)vinyl acetate and (poly)vinyl chloride; resorcinol resins; rubbers. such as polyisoprene. polybutadiene. butadiene-acrylonitrile rubber, butadienestyrene rubber, butyl rubber and neoprene rubber; ABS resins; and mixtures of such solid polymers.

Such normally flammable organic materials desirably are intimately mixed with the halogenated imidc fire hydrocarbyl I 4 retarding agent. This can be accomplished by any suitable means; eg. satisfactory results can be obtained with a solid polymer by employing an extruder, a 2-roll mill or a Banbury mixer. Optionally. one also may at this time incorporate in the resulting composition any desired fillers. pigments. plasticizers. antioxidants or.

other additives. It is often desirable to include one or more of the compounds of antimony. arsenic or bismuth. which are well known synergists for halogenated fire retardants. Antimony trioxide is highly effective and commonly used for this purpose.

While any effective amount of the halogenated and substituted-imide fire retarding agent can be employed to reduce flammability. it is generally desirable that this amount constitute from about 0.5 to about 20 wtf/r. preferably from about 1 wt.% to about 10 wtf/r of the total flame retardant composition. It is seldom advantageous to employ larger quantities of the fire retarding agent. except in the preparation of concentrates in which the agent may constitute 50 wt.% or

more of the composition. While the Oxygen Index. as

result when valid fire retarding agents are incorporated in the polymer. For example. minimum Oxygen Index values of about 23.8-24.0 are considered desirable for flame retardant compositions of polyethylene. polypropylene and polystyrene. When a metal compound sy nergist. such as antimony trioxide. also is incorporated in the composition..the synergist usually has a maximum effectiveness when the tire retarding agent to synergist weight ratio varies from about 0.5 to about 4. Another dcsirable constituent of the composition of this invention is .a stabilizer. preferably one of the well known and used vinyl stabilizers, such as an organotin compound. Stabilizers such as these are used to s'tabilize the'fire retarding agent against excessive thermal degradation and discoloration. Another benefit derived from the'use of a stabilizer is that corrosion of the metal processing equipment. due to liberation of halogens or halogen acids from the halogenated fire retarding agents, is minimized. A stabilizer, exemplified by an organotin compound. such as dibutyltin maleate. can be used in the range of about 0.05 to about 2.0 wt.%.

based on the total flame retardant composition, with a preferable range of from about 0.2 to about 1.0 wt.-%.

Because of the extraordinary fire retarding effectiveness of the substituted imides of this invention. both alone and in conjunction with a synergist, they can be used in far lower concentrations than previously known fire retardant materials of equivalent stability. The fact that acceptable levels of flame retardancy can be attained at unexpectedly low loadings of such substituted imide and synergist (with its inherent whitening power and opacity) in solid polymers. makes possible the preparation of polymer compositions having acceptable resistance to combustion and which largely retain the desirable physical characteristics of the pure polymer. It also facilitates coloring of such compositions and makes the preparation of concentrates practicable.

A. PREPARATION OF BROMINATED DlELS-ALDER ADDUCTS EXAMPLE I In a flask fitted with a stirrer, a thermometer and a reflux condenser was placed a mixture of 2.6 moles of maleic anhydride and 1 liter of ether. To the stirred mixture was added a solution ot2.6 moles of cyclopentadiene and 65 g. of heptane. in 50 ml. portions. at ambient temperature over a 5 hour period. Stirring was continued for 2 additional hours. The adduct product precipitated during this 7 hour period. The reaction mixture was then cooled to 10C.. filtered. and the precipitate obtained was dried. The precipitate. .a white crystalline material. weighed 364 grams and had a melting point of 1625C.

In a flask equipped with a stirrer. reflux condenser. thermometer. and additional funnel. was placed a mixture of 328 g. (2.0 moles) of the maleic 'anhydridecyclopentadiene adduct and 2 liters ofchlorot'orm. The mixture was stirred at ambient temperature. and 2 moles of bromine were added dropwise. During this ad dition. the temperature rose to 40C.. and this temperature was maintained by the addition rate of bromine. The additionperiod was 2 hours. followed by an additional hour of stirring. after which the reaction mixture was filtered. and the precipitate obtained was dried in a vacuum oven at ambient temperature. resulting in a product weighing 465 g. and having a melting point of 209-2l0C. The product. a white crystalline material. contained 48.8?! bromine (theory 49.371 bromine).

EXAMPLE 11 In a flask fitted with a stirrer. a thermometer and a reflux condenser was placed 5 moles of maleic anhydride and 25.4 moles of furan. (Furan was used as a solvent). The reaction mixture was stirred at ambient temperature for 6 hours. during which time the reaction temperature increased from ambient to about C. The adduct product precipitated during the reaction period. The'reaction mixture was then cooled to 15C..

filtered. and the precipitate obtained was dried. The

precipitate weighted 788 grams and had a melting point of 1 18C.

In a flask equipped with a stirrer. reflux condenser. thermometer. and additional funnel. was placed a mixture of 498 g. (3.0 moles) of the malcic anhydridefuran adduct and 3.4 liters of chloroform. The mixture was stirred at ambient temperature. and 3.0 moles of bromine were added drop wise. During this addition. the temperature rose to 40C and this temperature was maintained by the addition rate of bromine. The addition period was 6 hours. after which the reaction mixture was filtered. and the precipitate obtained was dried in a vacuum oven at ambient temperature. resulting in a product weighing 715 g. and having a melting point of 157C.. with decomposition starting at 278C. as measured by DTA.

EXAMPLE 111 Using the procedure of Example 1. the Diels-Alder adduct of maleic anhydride and butadiene was prepared and brominated. resulting in a solid product having a melting point of 200C.

In similar manner. using the same Diels-Alder adduct as above, chlorine was added to the residual unsaturation of the adduct.

B. PREPARATION OF lMlDES EXAMPLE lV Preparation of Phenyl-S,o-dibromonorbornane-2.3- dicarboxylic imide. 1

Into a 500 ml. flask were put 100 cc. of benzene and 0.05 moles of aniline. The reaction mixture was heated to reflux. and 0.05 moles of 5.6-dibromo-2.3- norbornane dicarhoxylic anhydride (the product of Example l) in warm benzene was added to the reaction mixture. The resultant mixture was refluxed for 1.5 hours. cooled toambient temperature and filtered. A quantitative yield of N-phenyl;5.6-dibromo-2- carboxynorbornane-3-carboxamide was isolated. with a melting point of l190C.

To a one liter flask equipped with a stirrer. reflux condenser and dropping funnelfwas charged 50 g. N- phenyl-5.6-dibromo-2 carboxynorbornane-3- carhoxamide and 300 cc. of chloroform. The mixture was stirred and 34cc. (0.46 mole) of SOClwas added over a 10 minute period. The mixture was heated to reflux and maintained at that temperature for 6 hours. i

The reaction mixture was cooled to ambient temperature and poured over ice. The resultant mixture was stirred for one hour and filtered. The product was successively washed with 1 portion of water and 2. separate portions of hot glacial acetic acid. The whitecrystalline material obtained was dried at 50C overnight. An 80% yield of N phenyl-5.6-dibromonorbornane-2.3- dicarboxylic imide was obtained. with a melting range of 300305C.. with,decomposition. Analysis: Calcu- 3922. N-3.3 /z'. The brominated phenyl imide has excellent thermal properties. i.e.. thermally stable. high melting point and low volatility. 1 1

EXAMPLE V a. Preparation of N-(allyl)-5.6-dibromonorbornane- 2.3-dicarboxylic imide.

Using the procedure ofExample IV. a 0.1 mole of 5.- 6-dibromonorbornane-Z.3-dicarboxylie anhydride was reacted with 0.1 mole allyl amine. The resultant carboxamide was treated with thionyl chloride. giving the N-allyl imide. melting at 196-200C.

i h. Preparation of N-(2.3-dibromopropyl)-5.6- dibromonorbornanel.3-dicarboxylic imide.

Since the N-allyl imide contained unsaturation. bromine was added to the compound to enhance the fire retarding properties.

To a flask equipped with a stirrer. reflux condenser. thermometer and additional funnel were charged 0.05 moles 18.3 g.) N-allyl5.6-dibrom0norbornane-2.3- dicarboxylic imide and 200 cc. of chloroform. To the stirred mixture was added 0.05 moles bromine. overa 1 hour period at ambient temperature. During the addition. the temperature increased to about 40C. The reaction mixture wasstirred for 1 hour after the comple tion of addition. cooled to 10C. and filtered. The crude product was isolated and recrystallized from glacial acetic acid. to give an 87% yield of N-(2.3-

- dibromopropyl)-5.o-dibromonorbornane-2.3

dicarboxylic imide. The product had a melting point of l70l78C.. bubbling at 240C. Analysis: Calculated for C H BnNO Br-6l7z. N2.67'7r; Found; Br- 60.7%. N-2.58'/1.

EXAMPLE Vl Preparation of N-benzy1-5.o-dibromonorbornane 2.3-dicarboxylic imide.

Using the procedure of Example IV. 5.6- dibromonorbornane-2.3-dicarboxylie anhydride was reacted, with benzylamine. N-benzyl-5.6- dibromonorbornane-2.3-dicarboxy1ie imide. having a melting point of 200202C.. was obtained. Analysis:

EXAMPLE w v EXAMPLE X 'The unsubstituted (on the nitrogen'atomj imide' was I I. 7 Preparation I of N p tolyl 5,6 d1hromonorhornanc prepmcdiusmg typlcul procedure by reuctmg the 9 i h 1 2H: brominated Diels-Alder adduct of maleic anhydride Using the Procedure of E a pl and hutadiene. in CHCI so'lution.with gaseous NH dibr )monorbornane-2.3-diearh x 'I' a h 'd 'd '2:

k O )1 IL In r1 L W 18 reacted with p-toluidlne. The product. N-p-tolvl-5.6- db m g b h l Byreacting sec. butylamlne with the bromlnated ad- 1 romonor nine-gt)- 7154f oxy 10 mn e. avinga duct ofvmuleic h dride and u m T n N-Substitutcd melting point of 50 5- C., was obtained. Analysis. imidc Containing a butyl group was prepared Calculated for l..H..-. O- -38.7'/1. N-.3.37 I X M E XII Found; Br-3x.2 N-3.3/1. A PL 15 The brommated adduct ofmaleic anhydride and EXAMPLE VIII furan (front Example II) reacted with aniIine.--forming g'. x o o L. Preparation of N-x-phenyI-S.6-dihromonorbornanci P g f 21 f 2.3-dicarboxylic imide p-bromo-. 2.5'dihromoor B. TESTING OF FIRERETARDANT IMIDES 2.4-dibromo-)v I i 7 A typical procedure for preparingflame. retardant To a 500 ml. resin kettle. equipped with a stirrer recompositions consists ofweighing the normally flamflux condenser and thermometer. were charged 0.1 mable organic material. Such 1 p ypropylene. nd mole of x-aniline. 1 mole 5,6-dibromonorbornanecharging I011 n cr at" 356F., The desired 2.3-dicarboxylic anhydride and 300 cc. of'CHCI The amount of synwcrglstg Suchils lm'tlmony trX1dreaction mixture was heated to reflux and refluxed for Added mlxcd etvcnly P The dcslrcd 1.5 hours. followed by cooling to ambient temperature. amount 9 the fire retarding f to the mixture in the Brabcnder. This mixture, along with any 'Then 4 moles SOCI were added to the cooled mixture d f 1/) h f n d h I if] f) 6 other additives. such as stabilizers or colorants. IS perm O 9 0 uxmg r mixed in the Brabender at .356F. for about l0m1nutes. hours. The reaction mixture was then cooled to arnbiw The wcllLmiXcd Composition is Compressed andmO-ldcd ent temperature and poured over ice. 'Ihe precipitate at and 40000 psig into a Slab approximately 2 formed was filtered and washed twice with 200 cc. porinches X 5 inches nud allowed to at ambient: tions of acetic acid. The product was dried in avaeuum m A i h- X 4 i h X 5 i h picel of h oven at C. over night. Yield and analytical data folmolded composition is then cut. and an Oxygen Index low: 5 determined, using ASTM -D-ZS63 procedure." I I Analysis i 4 Compound J Yield M.P. Theory Found C Br N Br N N-Parahrnmophenyl- 5.h-dihromonorhornune 2.3-dicarhoxyIic imide I C,,,H,. .Br,,N0. so 192-1924 53.x 3.! 47.8 2 7 N-Z.S-dIhromophenyI- 5.fv-dihromonorhornane- 2.3 diearhoxylic imidc C.,,H,,Br,N0. 86 292-300 60.2 2.2 5&5 2 1 N-Z.4-dibromophenyl- 5.6-dihromonorhornane 2.3-dicarhoxylic imide C, -,H,,I3r,NO. (10 300-302 60.2 2.2 56.6 23

, E A [X The following tablesexemplify typical formulations As a variation of part (b) of Example V, the N-allyl 50 and Oxygen Index data for various syntheticpoly'mers imide was chlorinated in the carbon-carbon unsaturaand fire retarding agents of this invention] TABLE I Run N0. A l 2 3 4 5 s 'Prolypropylene(g.) I00 88.5 88.5 94.0 92.5 92.0 94.0. 96.0

Polyethylene (g) I00 ABS (g) Impact Polystyrene (g) 100 Synergist Dihutyltin Stabilizer (g) t).

N-Phenyl Imide (g) 7.5 N-Propyl Imide" (g) Y Oxygen Index (ASTM-D-28o3-70) m0 17.x 19.4 ms 27.| 27

Flammability (UL-94) I I h ss-'2 $52 $15-2 SE-I S52 "Nphun \l-5.(Hlihrunumorhornane-Z.J-diearhoyylic imide. N-I 2.Ldihnnuopm yI l-5.(u-tlihnunonorhurnane-2.3-diearhox lie imide.

TABLE 11 l-LYALKATION ()1 FLAMI Rli'lARll-XNT (OMPOSl'llONS R1111 N1. 1 2 .1 17 1s 10 i0 :1 :3 :3 :4

Polypropylene (g) 1111) S515 14.1) 835 9-1.0 Polyethylene 1g.) 1011 711.7 70.8 ABS (g.) 100 (11s Synergist (511 0 (g.) I 3.7 2.1) 7.7 7.7 1-1.0 3.7 1.11 7.7 7.7 Dihutylin Stuhili/er 1g.) (1.1 N-p-Tolyl'lmide" (g.) Y 7.7 4.1) V N-Benzyl lmide"" 1g.) 7.7 4.1) 15.5 15. Oxygen lndex 11 .1) 17.8 19.4 20.) 25.5 1&4 26$) 25. 2(1 Flammability (UL H) SF: 'i- Si.- Si'.-: SF.- Si-.-.. 81-},

TABLE 111 EVALUATION OF FLAME RETARDANT COMPOSITIONS Run No. 1

Polypropylene (g.) 101) 91.0 92.2 91.2 84.2 84.2 71.2 74.7 74.7 Polyethylene (g.) 1111) 82.0 ABS (g.) 100 Y 70.0

Sy1'1ergist(Sh O.1)(g.) 6.1) 3.0 2.5 2.5 5.2 5.: s 10.7 4.5 4.5 N-p-bromophenyl lmitlc" (g.] 12.0 0.0 1&0 NZ,S-dihromophenyl v lmide (g.) 5.2 10.5 15.7 N-2,4-dihromophenyl lmidc (g.) 5.2 10.5 16.1) 15.7 Oxygen Index 18.0 17.8 19.4 24.8 27.5 26.2 26.2 27.2 7.6.9 27.11 29.11 26.5 26.9 Flammability (UL-94) SE2 SE2 SE-2 SE-IZ SE-I. SE-Z .SE Z SE-Z SE-Z SE-Z As noted from previous tables, certain substituted wherein R is hydrogen or methyl. and X is hydrogen. imides form desirable flame retardant compositions bromo. 0r l w I when used with certain synthetic polymers. Some of the 2. The compound of claim 1 which corresponds to preferred combinations are: the formula:

. 4O Polypropylene 21ml N-Phenyl lmlde Polypropylene and N-Propyl lmide Polypropylene and N-p-Bromophenyl lmide Polyethylene and N-Propyl lmide v Polyethylene and N-Benlyl lmitle ABS and N-Propyl lmitle c ABS and N-Dihromophenyl lmitle 4g N Z What we clzum 1s: g l. A compound corresponding to the formula: 0

F /N Z c 3. The compound of clzum 2 wherem L 1s phcnyl. ll 4.. The compound of claim 2 wherein Z is 2,3-

dihromopropyl. 5 I I wherein Z is hydrogen or a brominated. chlorinated. or The Compound Chum 2 l 3 unhalogenated hydrocarbon group selected from ey- Thc CUmpmmd of 2 wherein Z is y eloalkyl and alkyl having up to 8 carbons. allyl. benzyl. The compound of Chum 2 wherein Z 15 P phenyl or methylphenyl, and Y has one of the strucbromophenyltures; 6O 8. The compound of claim 2 wherein Z is 2.5-

dibromophenyl. R R R 9. The compound of claim 2 wherein Z is 2.4- Br Br Br dihromophenyl.

O 10. The compound of claim 2 wherein Z is 21 chlorinated hen lor meth l hen l. X X P y :k y P Y T52 3? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION g Patent 3,903,109 Dated Sept. 2, 1975 Inventor(s) Anderson 0. Dotson, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

0n page I left hand column, line 7, the name of the assignee should "I read--C1'ties Service Company-. C01 umn 8, line 31 "nad" shou] d read --and--.

Signed and Sealed this twenty-fifth D3) Of November 1975 [SEAL] Attest:

RUTH C. MASON I C. MARSHALL DANN Arresting Officer Commissioner of Patents and Trademarks 

1. A COMPOUND CORRESPONDING TO THE FORMULA:
 2. The compound of claim 1 which corresponds to the formula:
 3. The compound of claim 2 wherein Z is phenyl.
 4. The compound of claim 2 wherein Z is 2,3-dibromopropyl.
 5. The compound of claim 2 wherein Z is tolyl.
 6. The compound of claim 2 wherein Z is benzyl.
 7. The compound of claim 2 wherein Z is p-bromophenyl.
 8. The compound of claim 2 wherein Z is 2,5-dibromophenyl.
 9. The compound of claim 2 wherein Z is 2,4-dibromophenyl.
 10. The compound of claim 2 wherein Z is a chlorinated phenyl or methyl phenyl. 